KR20210144348A - Olefin based polymer - Google Patents

Abstract

The present invention relates to an olefin-based polymer satisfying the conditions of: (1) a melt index (MI, 190℃ 2.16 kg load) of 0.1-10.0 g/10 minutes; (2) a density (d) of 0.855-0.880 g/cc; (3) a melting point (Tm) of 30-60℃, as determined from a DSC curve obtained by differential scanning calorimetry (DSC); and (4) 20<=T(90)-T(50)<=27 and 4.5<=T(95)-T(90)<=7.0, as determined by successive self-nucleation/annealing (SSA). The olefin-based polymer according to the present invention shows reduced crystalline segment distribution, and thus shows excellent anti-blocking property.

Description

Olefin-based polymer {OLEFIN BASED POLYMER}

The present invention relates to an olefin-based polymer, and more particularly, to an olefin-based polymer exhibiting excellent anti-blocking properties by reducing the distribution of crystalline regions.

Polyolefin has excellent moldability, heat resistance, mechanical properties, sanitary quality, water vapor permeability and appearance characteristics of molded products, and is widely used for extrusion molded products, blow molded products and injection molded products. However, polyolefins, particularly polyethylene, have low compatibility with polar resins such as nylon and low adhesion to polar resins and metals because there is no polar group in the molecule. As a result, it has been difficult to blend polyolefins with polar resins or metals or laminate them with these materials. In addition, molded articles of polyolefin have problems with low surface hydrophilicity and antistatic properties.

In order to solve this problem and increase affinity for a polar material, a method of grafting a polar group-containing monomer onto a polyolefin through radical polymerization has been widely used. However, in this method, intramolecular crosslinking of polyolefin and cleavage of molecular chains occurred during the graft reaction, so that the viscosity balance between the graft polymer and the polar resin was poor, and miscibility was low. In addition, there was a problem in that the appearance characteristics of the molded article were low due to the gel component generated by intramolecular crosslinking or foreign substances generated by the cleavage of molecular chains.

In addition, as a method for producing an olefin polymer such as an ethylene homopolymer, an ethylene/α-olefin copolymer, a propylene homopolymer or a propylene/α-olefin copolymer, a polar monomer is copolymerized under a metal catalyst such as a titanium catalyst or a vanadium catalyst. method was used. However, when the polar monomer is copolymerized using the metal catalyst as described above, there is a problem in that the molecular weight distribution or composition distribution is wide and the polymerization activity is low.

Also, as another method, a method of polymerization in the presence of a metallocene catalyst composed of a transition metal compound such as zircononocene dichloride and an organoaluminum oxy compound (aluminoxane) is known. When a metallocene catalyst is used, a high molecular weight olefin polymer is obtained with high activity, and the resulting olefin polymer has a narrow molecular weight distribution and a narrow composition distribution.

In addition, using a non-crosslinked cyclopentadienyl group, a crosslinked or uncrosslinked bisindenyl group, or a metallocene compound having a ligand of an ethylene bridged unsubstituted indenyl group/fluorenyl group as a catalyst, a polyolefin containing a polar group is prepared. As the method, a method using a metallocene catalyst is also known. However, these methods have the disadvantage of very low polymerization activity. For this reason, although a method of protecting a polar group with a protecting group has been implemented, when a protecting group is introduced, the protecting group must be removed again after the reaction, thereby complicating the process.

The ansa-metallocene compound is an organometallic compound including two ligands connected to each other by a bridge group, and rotation of the ligand is prevented by the bridge group, and the activity of the metal center and structure is determined.

Such an ansa-metallocene compound is used as a catalyst in the preparation of an olefin-based homopolymer or copolymer. In particular, it is known that an ansa-metallocene compound containing a cyclopentadienyl-fluorenyl ligand can produce polyethylene having a high molecular weight, thereby controlling the microstructure of polyethylene. .

In addition, it is known that the ansa-metallocene compound containing an indenyl ligand has excellent activity and can prepare polyolefins with improved stereoregularity.

As such, various studies have been made on ansa-metallocene compounds capable of controlling the microstructure of olefinic polymers while having higher activity, but the degree is still insufficient.

KR 288272 B1 KR 2007-0003071 A

An object to be solved by the present invention is to provide an olefin-based polymer that exhibits excellent anti-blocking properties by reducing the distribution of crystalline regions obtained by polymerizing an olefin-based monomer while introducing hydrogen gas using a transition metal compound catalyst. .

In order to solve the above problems, the present invention provides an olefin-based polymer satisfying the requirements of the following (1) to (4).

(1) Melt Index (MI, 190 ° C. 2.16 kg load condition) 0.1 g/10 min to 10.0 g/10 min, (2) Density (d) is 0.855 g/cc to 0.880 g/cc, (3) the melting temperature (Tm) obtained from the DSC curve obtained by measuring with a differential scanning calorimeter (DSC) is 30°C to 60°C, (4) 20≤T(90)- T(50)≤27, 4.5≤T(95)-T(90)≤7.0, where T(50), T(90) and T(95) are the differential scanning calorimetry precision (SSA) measurements, respectively. The temperature at which 50%, 90%, and 95% melt respectively when the temperature-heat capacity curve is fractionated from the result.

The olefin-based polymer according to the present invention exhibits excellent anti-blocking properties due to reduced distribution of crystalline regions.

1 is a graph showing the results of measurement of the polymer of Example 1 by differential scanning calorimetry precision measurement (SSA).
2 is a graph showing the fractionation results of differential scanning calorimetry (SSA) for the polymer of Example 1 and T(50) and T(90).
3 is a graph showing the results of measurement of the polymer of Comparative Example 1 by differential scanning calorimetry precision measurement (SSA).
4 is a graph showing T(50) and T(90) of the polymer of Comparative Example 1 after fractionation of the results measured by differential scanning calorimetry (SSA).

Hereinafter, the present invention will be described in more detail to help the understanding of the present invention.

The terms or words used in the present specification and claims should not be construed as being limited to their ordinary or dictionary meanings, and the inventor may properly define the concept of the term in order to best describe his invention. It should be interpreted as meaning and concept consistent with the technical idea of the present invention based on the principle that there is.

As used herein, the term "polymer" means a polymer compound prepared by polymerization of monomers of the same or different types. The generic term "polymer" includes the terms "homopolymer", "copolymer", "terpolymer" as well as "interpolymer". Also, the term “interpolymer” refers to a polymer prepared by polymerization of two or more different types of monomers. The generic term "interpolymer" refers to the term "copolymer" (which is commonly used to refer to polymers made from two different monomers), as well as the term "copolymer" (which is commonly used to refer to polymers prepared from three different types of monomers). used) the term "terpolymer". This includes polymers prepared by the polymerization of four or more types of monomers.

The olefin-based polymer according to the present invention satisfies the requirements of the following (1) to (4).

(1) Melt Index (MI, 190 ° C. 2.16 kg load condition) 0.1 g/10 min to 10.0 g/10 min, (2) Density (d) is 0.855 g/cc to 0.880 g/cc, (3) the melting temperature (Tm) obtained from the DSC curve obtained by measuring with a differential scanning calorimeter (DSC) is 30°C to 60°C, (4) 20≤T(90)- T(50)≤27, 4.5≤T(95)-T(90)≤7.0, where T(50), T(90) and T(95) are the differential scanning calorimetry precision (SSA) measurements, respectively. The temperature at which 50%, 90%, and 95% melt respectively when the temperature-heat capacity curve is fractionated from the result.

The olefin-based polymer according to the present invention has a low density, and has a reduced distribution of crystalline regions compared to a conventional conventional olefin-based polymer, so that the density and melt index at the same level (Melt Index, MI, 190°C, 2.16 kg load condition) When it has, it exhibits more excellent anti-blocking properties. The olefin-based polymer according to the present invention is prepared by a manufacturing method comprising the step of polymerizing an olefin-based monomer by introducing hydrogen gas in the presence of a catalyst composition for olefin polymerization, and has a narrow distribution according to hydrogen gas input during polymerization. The crystalline region is introduced to exhibit excellent anti-blocking properties.

The melt index (MI) can be adjusted by controlling the amount of the catalyst used in the process of polymerizing the olefin-based polymer for comonomer, and affects the mechanical properties and impact strength, and moldability of the olefin-based polymer. In the present specification, the melt index is measured at 190 ° C., 2.16 kg load condition according to ASTM D1238 under low density conditions of 0.855 g / cc to 0.880 g / cc, 0.1 g / 10 minutes to 10 g / 10 minutes and specifically 0.3 g/10 min to 9.0 g/10 min, more specifically 1.0 g/10 min to 6.5 g/10 min.

Meanwhile, the density may be 0.855 g/cc to 0.880 g/cc, and specifically 0.860 g/cc to 0.880 g/cc.

In general, the density of the olefin-based polymer is affected by the type and content of the monomer used during polymerization, the degree of polymerization, and the like. The olefin-based polymer of the present invention is polymerized using a catalyst composition containing a transition metal compound having a characteristic structure, and a large amount of comonomer can be introduced. can have

In addition, the olefin-based polymer has a melting temperature (Tm) obtained from a DSC curve obtained by measuring with a differential scanning calorimeter (DSC) of 30°C to 60°C, specifically 30°C to 55°C, more specifically 35°C to 50°C can be

In addition, the olefin-based polymer is 20≤T(90)-T(50)≤27, 4.5≤T(95)-T(90)≤7.0, specifically 23 when measured by differential scanning calorimetry (SSA). ≤T(90)-T(50)≤27, 5.0≤T(95)-T(90)≤7.0, more specifically 25≤T(90)-T(50)≤27, 5.0 ≤ T(95)-T(90) ≤ 6.5.

The T(50), T(90) and T(95) are respectively 50%, 90%, and 95% melted when the temperature-heat capacity curve is fractionated from the differential scanning calorimetry precision measurement (SSA) measurement result, respectively. is the temperature

In general, the melting temperature (Tm) measurement using a differential scanning calorimeter (DSC) is heated at a constant rate to a temperature approximately 30°C higher than the melting temperature (Tm), and then is approximately 30°C lower than the glass transition temperature (Tg). After the first cycle of cooling at a constant rate to The differential scanning calorimeter precision measurement (SSA) measurement is performed using a differential scanning calorimeter (DSC) after the first cycle to a temperature just before the peak of the melting temperature (Tm) and cooled to a temperature lowered by about 5°C. It is a method to obtain more precise crystal information by repeatedly performing heating and cooling processes (Eur. Polym. J. 2015, 65, 132).

When a small amount of highly crystalline region is introduced into the olefin-based polymer, it does not appear when measuring the melting temperature using a general differential scanning calorimeter (DSC), and the high-temperature melting peak can be measured through the differential scanning calorimetry precision measurement (SSA).

In addition, the olefin-based polymer according to an example of the present invention may further satisfy the requirement of (5) a weight average molecular weight (Mw) of 10,000 g/mol to 500,000 g/mol, and specifically, the weight average molecular weight (Mw) is 30,000 g/mol to 300,000 g/mol, more specifically 50,000 g/mol to 200,000 g/mol. In the present invention, the weight average molecular weight (Mw) is a polystyrene equivalent molecular weight analyzed by gel permeation chromatography (GPC).

In addition, the olefin-based polymer according to an example of the present invention additionally has a ratio (Mw/Mn) of a weight average molecular weight (Mw) to a number average molecular weight (Mn) (6) Molecular Weight Distribution (MWD) of 0.1 to 6.0 The phosphorus requirement may be satisfied, and the molecular weight distribution (MWD) may be specifically 1.0 to 4.0, more specifically 2.0 to 3.0.

In addition, the olefin-based polymer according to an example of the present invention may additionally satisfy the requirement of (7) a melt flow rate ratio (MFRR) of 3 to 7, and the melt flow rate ratio (MFRR) may be specifically 4 to 7, More specifically, it may be 6.4 to 6.8.

The melt flow rate ratio (MFRR) _{means the ratio obtained by dividing MI 10} (melt index under a load of 10 kg and 190° C.) by MI _2.16 (melt index under a load of 2.16 kg and 190° C.) of the long side chain (LCB) of the polymer. As the number decreases, the MFRR may exhibit a low value, and mechanical properties of the polymer may be improved.

The olefin-based polymer is an olefin-based monomer, specifically, an alpha-olefin-based monomer, a cyclic olefin-based monomer, a diene olefin-based monomer, a triene olefin-based monomer, and a styrenic monomer, or 2 It may be a copolymer of more than one species. More specifically, the olefin-based polymer may be a copolymer of ethylene and an alpha-olefin having 3 to 12 carbon atoms or a copolymer of ethylene and an alpha-olefin having 3 to 10 carbon atoms.

The alpha-olefin comonomer is propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene , 1-tetradecene, 1-hexadecene, 1-aitocene, norbornene, norbornadiene, ethylidene noboden, phenyl noboden, vinyl noboden, dicyclopentadiene, 1,4-butadiene, 1,5 - It may include any one or a mixture of two or more selected from the group consisting of -pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, and 3-chloromethylstyrene.

More specifically, the olefin copolymer according to an example of the present invention may be a copolymer of ethylene and propylene, ethylene and 1-butene, ethylene and 1-hexene, ethylene and 4-methyl-1-pentene, or ethylene and 1-octene. And, more specifically, the olefin copolymer according to an example of the present invention may be a copolymer of ethylene and 1-butene.

When the olefinic polymer is a copolymer of ethylene and alpha-olefin, the amount of the alpha-olefin is 90 wt% or less, more specifically 70 wt% or less, and even more specifically 5 wt% to 60 wt% based on the total weight of the copolymer. It may be weight %, and more specifically, it may be 20 weight % to 50 weight %. When the alpha-olefin is included in the above range, it is easy to implement the above-described physical properties.

The olefin-based polymer according to an embodiment of the present invention having the above physical properties and structural characteristics, hydrogen gas is introduced in the presence of a metallocene catalyst composition including one or more transition metal compounds in a single reactor, and the olefin-based polymer It can be prepared through a continuous solution polymerization reaction that polymerizes the monomers. Accordingly, in the olefin-based polymer according to an embodiment of the present invention, a block is not formed in which two or more repeating units derived from any one of the monomers constituting the polymer in the polymer are linearly connected. That is, the olefin-based polymer according to the present invention does not contain a block copolymer, and is selected from the group consisting of a random copolymer, an alternating copolymer, and a graft copolymer. and, more specifically, may be a random copolymer.

Specifically, the olefinic copolymer of the present invention is obtained by a manufacturing method comprising the step of polymerizing an olefinic monomer by introducing hydrogen gas in the presence of a catalyst composition for olefin polymerization comprising a transition metal compound of Formula 1 below can get

The amount of the hydrogen gas may be 10 to 60 sccm, specifically 15 to 50 sccm, and more specifically 20 to 40 sccm. When the amount of hydrogen gas input in the step of polymerizing the olefin monomer satisfies the above range, an olefin-based polymer satisfying the requirements of (1) to (4) of the present invention may be prepared.

However, in the preparation of the olefin-based polymer according to an embodiment of the present invention, the scope of the structure of the transition metal compound of Formula 1 is not limited to the specific disclosed form, and all changes included in the spirit and technical scope of the present invention; It should be understood to include equivalents and substitutes.

[Formula 1]

R ₁ to R ₁₃ are each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; alkoxy having 1 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; arylalkoxy having 7 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; arylalkyl having 7 to 20 carbon atoms; silyl; or silyl having 1 to 3 substituents selected from the group consisting of alkyl having 1 to 12 carbon atoms and alkoxy having 1 to 12 carbon atoms, wherein _{two or more adjacent to each other among R 1} to R ₁₂ are connected to each other to form a ring can,

X and X' are each independently O, S or a linking group,

A is alkylene having 1 to 6 carbon atoms,

Y is C or Si,

M is a group 4 transition metal,

Q is hydrogen; halogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; arylalkyl having 7 to 20 carbon atoms; alkylamino having 1 to 20 carbon atoms; or arylamino having 6 to 20 carbon atoms.

When the transition metal compound is used as a catalyst and applied to olefin polymerization, polyolefins having characteristics such as high molecular weight can be prepared by exhibiting high activity even at high polymerization temperatures and exhibiting high copolymerizability. In particular, it is possible to prepare a low-density olefin-based polymer having a high molecular weight density of 0.855 g/cc to 0.880 g/cc due to the structural characteristics of the catalyst.

In addition, in the transition metal compound of Formula 1 according to an exemplary embodiment of the present invention, R ₁ to R ₁₂ are each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; alkoxy having 1 to 20 carbon atoms; silyl; or silyl having 1 to 3 substituents selected from the group consisting of alkyl having 1 to 12 carbon atoms and alkoxy having 1 to 12 carbon atoms, wherein _{two or more of R 1} to R ₁₂ are connected to each other to form a ring can form,

wherein R ₁₃ is hydrogen; halogen; alkyl having 1 to 12 carbon atoms; cycloalkyl having 3 to 12 carbon atoms; aryl having 6 to 12 carbon atoms; alkylaryl having 7 to 12 carbon atoms; Or it may be an arylalkyl having 7 to 12 carbon atoms,

Wherein X and X' may each independently be O, S or a linking group,

wherein A is alkylene having 1 to 6 carbon atoms,

Y may be C or Si,

M may be Ti, Zr or Hf,

wherein Q is hydrogen; halogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; Or it may be an arylalkyl having 7 to 20 carbon atoms.

In addition, in the transition metal compound of Formula 1 according to another example of the present invention, R ₁ to R ₁₂ are each independently hydrogen; alkyl having 1 to 12 carbon atoms; cycloalkyl having 3 to 12 carbon atoms; silyl; or silyl having 1 to 3 substituents selected from the group consisting of alkyl having 1 to 12 carbon atoms and alkoxy having 1 to 12 carbon atoms, wherein _{two or more of R 1} to R ₁₂ are connected to each other to form a ring can form,

wherein R ₁₃ is hydrogen; alkyl having 1 to 12 carbon atoms; aryl having 6 to 12 carbon atoms; or an alkylaryl having 7 to 12 carbon atoms; Or it may be an arylalkyl having 7 to 12 carbon atoms,

Wherein X and X' may each independently be O, S or a linking group,

A may be an alkylene having 1 to 6 carbon atoms,

Y may be C or Si,

M may be Ti, Zr or Hf,

wherein Q is hydrogen; halogen; alkyl having 1 to 12 carbon atoms; It may be a cycloalkyl having 3 to 12 carbon atoms.

In an example of the present invention, the transition metal compound of Formula 1 may be a transition metal compound represented by Formula 1a below.

[Formula 1a]

In Formula 1a, R ₁ to R ₁₃ , X, X', M, Y, and Q are each as defined in Formula 1 above, and n is an integer of 1, 2, or 3.

In addition, in an example of the present invention, the transition metal compound of Formula 1 may be a compound specifically represented by Formula 2 below.

[Formula 2]

In Formula 2,

R ₁ to R ₄ , R ₅ , R ₈ , R ₉ and R ₁₂ may each independently be hydrogen or alkyl having 1 to 12 carbon atoms,

R ₁₃ is hydrogen, alkyl having 1 to 12 carbon atoms, aryl having 6 to 12 carbon atoms; Or it may be an alkylaryl having 7 to 12 carbon atoms,

R ₁₄ to R ₂₁ may each independently be hydrogen or alkyl having 1 to 6 carbon atoms,

X and X' may each independently be O, S or a linking group,

A may be an alkylene having 1 to 6 carbon atoms,

Y may be C or Si,

M may be Hf,

Q may be halogen or alkyl having 1 to 12 carbon atoms,

n may be 1, 2, or 3.

In addition, in the transition metal compound of Formula 2,

The R ₁ to R ₄ , R ₅ , R ₈ , R ₉ and R ₁₂ may be hydrogen,

Wherein R ₁₃ may be an aryl having 6 to 12 carbon atoms,

Wherein X and X' may each independently be O, S or a linking group,

A may be ethylene,

Y may be C,

M may be Hf,

Wherein Q may be an alkyl having 1 to 6 carbon atoms,

The n may be 1.

In one example of the present invention, the transition metal compound of Formula 2 may be a transition metal compound represented by the following Formula 2a.

[Formula 2a]

In Formula 1a, R ₁ to R ₁₃ , X, X', M, Y, and Q are each as defined in Formula 1 above, and n is an integer of 1, 2, or 3. Also, n may be 1.

The compound represented by Formula 1 may be specifically a compound represented by any one of Formulas 1-1 and 1-2.

[Formula 1-1]

[Formula 1-2]

Each of the substituents defined in the present specification will be described in detail as follows.

As used herein, the term 'halogen' means fluorine, chlorine, bromine or iodine, unless otherwise noted.

As used herein, unless otherwise stated, the term 'alkyl' refers to a straight-chain, cyclic or branched hydrocarbon residue, without limitation, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl , t-butyl, n-pentyl, isopentyl and hexyl.

The term 'cycloalkyl' as used herein, unless otherwise stated, refers to a non-aromatic cyclic hydrocarbon radical composed of carbon atoms. 'Cycloalkyl' includes, by way of non-limiting example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl.

The term 'aryl' as used herein, unless otherwise stated, refers to an optionally substituted benzene ring, or to a ring system that can be formed by fusing one or more optional substituents. Exemplary optional substituents include substituted C _1-3 alkyl, substituted C _2-3 alkenyl, substituted C _2-3 alkynyl, heteroaryl, heterocyclic, aryl, optionally having 1 to 3 fluorine substituents. Alkoxy, aryloxy, aralkoxy, acyl, aroyl, heteroaroyl, acyloxy, aroyloxy, heteroaroyloxy, sulfanyl, sulfinyl, sulfonyl, aminosulfonyl, sulfonylamino, carboxyamide, amino carbonyl, carboxy, oxo, hydroxy, mercapto, amino, nitro, cyano, halogen or ureido. Such rings or ring systems may optionally be fused to an aryl ring (eg, a benzene ring), carbocyclic ring or heterocyclic ring optionally having one or more substituents. Examples of 'aryl' groups include, but are not limited to, phenyl, naphthyl, tetrahydronaphthyl, biphenyl, indanyl, anthracyl or phenanthryl, and substituted derivatives thereof.

As used herein, the term 'alkenyl' refers to a straight or branched chain hydrocarbon radical having one or more carbon-carbon double bonds. Examples of 'alkenyl' as used herein include, but are not limited to, ethenyl and propenyl.

As used herein, the term 'alkoxy' refers to the group _{-OR a , wherein R a} is alkyl as defined above. 'Alkoxy' includes, but is not limited to, methoxy, difluoromethoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy and t-butoxy.

In the present specification, 'silyl' means an unsubstituted silyl or a silyl group substituted with one or more substituents. 'Silyl' includes, but is not limited to, silyl, trimethylsilyl, triethylsilyl, isopropyldimethylsilyl, t-butyldimethylsilyl, t-butyldiphenylsilyl, hexyldimethylsilyl, methoxymethylsilyl, (2-methoxyethoxy ) methylsilyl, trimethoxysilyl, and triethoxysilyl.

The transition metal compound of Formula 1 may be used as a catalyst for a polymerization reaction in the form of a catalyst composition including one or more compounds of Formulas 3 to 5 as a co-catalyst.

[Formula 3]

-[Al(R ₂₂ )-O] _a -

[Formula 4]

A(R ₂₂ ) ₃

[Formula 4]

[LH] ⁺ [W(D) ₄ ] ^- or [L] ⁺ [W(D) ₄ ] ^-

In Formulas 2 to 3,

R ₂₂ may be the same or different from each other, and are each independently selected from the group consisting of halogen, hydrocarbyl having 1 to 20 carbon atoms, and hydrocarbyl having 1 to 20 carbon atoms substituted with halogen,

A is aluminum or boron,

D is each independently aryl having 6 to 20 carbon atoms or alkyl having 1 to 20 carbon atoms in which one or more hydrogen atoms may be substituted with a substituent, wherein the substituent is halogen, hydrocarbyl having 1 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms and at least one selected from the group consisting of aryloxy having 6 to 20 carbon atoms,

H is a hydrogen atom,

L is a neutral or cationic Lewis base,

W is a group 13 element,

a is an integer greater than or equal to 2;

Examples of the compound represented by Formula 3 include alkylaluminoxanes such as methylaluminoxane (MAO), ethylaluminoxane, isobutylaluminoxane, and butylaluminoxane, and two or more kinds of the alkylaluminoxane are mixed and modified alkylaluminoxane, and specifically may be methylaluminoxane and modified methylaluminoxane (MMAO).

Examples of the compound represented by Formula 4 include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum , tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron, and the like, and specifically may be selected from trimethyl aluminum, triethyl aluminum, and triisobutyl aluminum.

Examples of the compound represented by Formula 5 include triethylammoniumtetraphenylboron, tributylammoniumtetraphenylboron, trimethylammoniumtetraphenylboron, tripropylammoniumtetraphenylboron, trimethylammoniumtetra(p-tolyl)boron, and trimethylammoniumtetra (o,p-dimethylphenyl)boron, tributylammoniumtetra(p-trifluoromethylphenyl)boron, trimethylammoniumtetra(p-trifluoromethylphenyl)boron, tributylammoniumtetrapentafluorophenylboron, N,N -diethylaniliniumtetraphenylboron, N,N-diethylaniliniumtetrapentafluorophenylboron, diethylammoniumtetrapentafluorophenylboron, triphenylphosphoniumtetraphenylboron, trimethylphosphoniumtetraphenylboron, dimethyl Anilinium tetrakis(pentafluorophenyl)borate, triethylammoniumtetraphenylaluminum, tributylammoniumtetraphenylaluminum, trimethylammoniumtetraphenylaluminum, tripropylammoniumtetraphenylaluminum, trimethylammoniumtetra(p-tolyl)aluminum, tri Propylammonium tetra(p-tolyl)aluminum, triethylammoniumtetra(o,p-dimethylphenyl)aluminum, tributylammoniumtetra(p-trifluoromethylphenyl)aluminum, trimethylammoniumtetra(p-trifluoromethylphenyl)aluminum , tributylammoniumtetrapentafluorophenylaluminum, N,N-diethylaniliniumtetraphenylaluminum, N,N-diethylaniliniumtetrapentafluorophenylaluminum, diethylammoniumtetrapentafluorophenylaluminum, triphenyl Phosphonium tetraphenylaluminum, trimethylphosphoniumtetraphenylaluminum, tripropylammonium tetra(p-tolyl)boron, triethylammoniumtetra(o,p-dimethylphenyl)boron, triphenylcarboniumtetra(p-trifluoromethylphenyl) ) boron or triphenylcarboniumtetrapentafluorophenylboron.

The catalyst composition, as a first method, 1) contacting the transition metal compound represented by Formula 1 with the compound represented by Formula 3 or Formula 4 to obtain a mixture; and 2) adding the compound represented by Formula 5 to the mixture.

In addition, the catalyst composition may be prepared by contacting the transition metal compound represented by Formula 1 with the compound represented by Formula 5 as a second method.

In the case of the first method among the methods for preparing the catalyst composition, the molar ratio of the compound represented by Formula 4 or Formula 5 to the transition metal compound represented by Formula 1 and the transition metal compound represented by Formula 3 is 1 It may be from 2 to 1:5,000, specifically from 1:10 to 1:1,000, and more specifically from 1:20 to 1:500. When the molar ratio of the compound represented by Formula 3 or Formula 4 to the transition metal compound represented by Formula 1 is less than 1:2, the amount of the alkylating agent is very small, and there is a problem that the alkylation of the metal compound cannot proceed completely, When the ratio exceeds 1:5,000, the metal compound is alkylated, but there is a problem in that the alkylated metal compound cannot be completely activated due to a side reaction between the remaining excess alkylating agent and the activator, which is the compound of Formula 5. In addition, the molar ratio of the compound represented by Formula 5 to the transition metal compound represented by Formula 1 may be 1:1 to 1:25, specifically 1:1 to 1:10, and more specifically It may be 1:1 to 1:5. When the molar ratio of the compound represented by Formula 5 to the transition metal compound represented by Formula 1 is less than 1:1, the amount of the activator is relatively small, and the activation of the metal compound is not completely achieved, so the activity of the catalyst composition produced may fall, and if the molar ratio is more than 1:25, the metal compound is fully activated, but the unit price of the catalyst composition may not be economical or the purity of the resulting polymer may be deteriorated with an excess of the remaining activator.

In the case of the second method among the methods for preparing the catalyst composition, the molar ratio of the compound represented by Formula 5 to the transition metal compound of Formula 1 may be 1:1 to 1:500, specifically 1:1 to 1: 50, and more specifically 1:2 to 1:25. When the molar ratio is less than 1:1, the amount of the activator is relatively small, so that the activation of the metal compound is not completely achieved, so there is a problem in that the activity of the resulting catalyst composition is decreased, and when it is more than 1:500, the activation of the metal compound is not achieved Although complete, there is a problem in that the unit price of the catalyst composition is not economically low with the excess amount of activator remaining, or the purity of the resulting polymer is lowered.

A hydrocarbon solvent such as pentane, hexane, heptane, or the like, or an aromatic solvent such as benzene, toluene, etc. may be used as the reaction solvent in the preparation of the catalyst composition, but is not limited thereto, and all solvents available in the art are used. can be used

In addition, the catalyst composition may include the transition metal compound and the cocatalyst compound in a supported form on a carrier.

The carrier may be used without particular limitation as long as it is used as a carrier in a metallocene-based catalyst. Specifically, the carrier may be silica, silica-alumina or silica-magnesia, and any one or a mixture of two or more thereof may be used.

Among them, when the carrier is silica, since the functional group of the silica carrier and the metallocene compound of Formula 1 chemically forms a bond, there is almost no catalyst released from the surface during olefin polymerization. As a result, it is possible to prevent the occurrence of fouling in which the reactor wall surface or polymer particles are agglomerated during the production process of the olefin-based polymer. In addition, the olefin-based polymer prepared in the presence of the catalyst including the silica carrier has excellent particle shape and apparent density of the polymer.

More specifically, the carrier may be high-temperature dried silica or silica-alumina containing a siloxane group having high reactivity on the surface through a method such as high-temperature drying.

The carrier may further include an oxide, carbonate, sulfate or nitrate component such as _{Na 2} O, K ₂ CO ₃ , BaSO ₄ or Mg(NO ₃ ) _{2 .}

The polymerization reaction for polymerizing the olefinic monomer may be performed by a conventional process applied to polymerization of the olefinic monomer, such as continuous solution polymerization, bulk polymerization, suspension polymerization, slurry polymerization, or emulsion polymerization.

The polymerization reaction of the olefin monomer may be performed under an inert solvent, and examples of the inert solvent include benzene, toluene, xylene, cumene, heptane, cyclohexane, methylcyclohexane, methylcyclopentane, n-hexane, 1-hexene, 1-octene, but not limited thereto.

The polymerization of the olefin-based polymer may be made at a temperature of about 25 °C to about 500 °C, specifically 80 °C to 250 °C, more preferably at a temperature of 100 °C to 200 °C. In addition, the reaction pressure during polymerization is 1 kgf/cm ² to 150 kgf/cm ² , preferably 1 kgf/cm ² to 120 kgf/cm ² , more preferably 5 kgf/cm ² to 100 kgf/cm ² can be

Since the olefin-based polymer of the present invention has improved physical properties, it is used for blow molding and extrusion in various fields and uses such as materials for automobiles, electric wires, toys, textiles, medical materials, etc. It is useful for molding or injection molding, and in particular, it can be usefully used for automobiles requiring excellent impact strength.

In addition, the olefin-based polymer of the present invention may be usefully used in the production of a molded article.

Specifically, the molded article may be a blow molding molded article, an inflation molded article, a cast molded article, an extrusion laminate molded article, an extrusion molded article, an expanded molded article, an injection molded article, a sheet, a film, a fiber, a monofilament, or a nonwoven fabric.

Example

Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily carry out the present invention. However, the present invention may be embodied in many different forms and is not limited to the embodiments described herein.

Synthesis of ligands and transition metal compounds

Organic reagents and solvents were purchased from Aldrich, and purified by standard methods unless otherwise specified. The reproducibility of the experiment was improved by blocking the contact of air and moisture at all stages of the synthesis.

Preparation Example 1: Preparation of Ligand Compound and Transition Metal Compound

Step 1: Preparation of ((ethane-1,2-diylbis(oxy))bis(4,1-phenylene))bis(phenylmethanone)

1,2-diphenoxyethane (5.25 g, 24.5 mmol), AlCl ₃ (7.20 g) and 1,2-dichloroethane (87.5 mL) were placed in a 100 mL Schlenk flask. Benzoyl chloride (2.05 eq, 7.06 g) was slowly added dropwise at room temperature. Stir overnight at 65°C. Then, the final compound was obtained by extraction using ice water, 10% HCl, and distilled water.

¹ H NMR (CDCl ₃ ): 7.86 (d, 4H), 7.77 (d, 4H), 7.58 (m, 2H), 7.50 (m, 4H), 7.04 (d, 4H), 4.56 (s, 4H)

Step 2: Preparation of 1,2-bis(4-(cyclopenta-2,4-dien-1-ylidene(phenyl)methyl)phenoxy)ethane)

((ethane-1,2-diylbis(oxy))bis(4,1-phenylene))bis(phenylmethanone) (4.0g, 7.47mmol) prepared in step 1 in a 100 mL Schlenk flask, Pyrrolidine (2.4 mL) and THF (8.9 mL) were added. Sodium cyclopentadienide (sodium Cp) (2.0 M, 28.4 mL) was slowly added dropwise at room temperature. It was stirred at room temperature overnight. After extraction using distilled water and diethyl ether, the final compound was obtained through recrystallization of methanol.

¹ H NMR (CDCl ₃ ): 7.41 (m, 6H), 7.34 (m, 8H), 6.99 (d, 4H), 6.63 (d, 4H), 6.37 (s, 2H), 6.28 (s, 2H), 4.42 (s, 4H)

Step 3: 1,2-bis(4-(cyclopenta-2,4-dien-1-yl(1,1,4,4,7,7,10,10-octamethyl-2,3,4, Preparation of 7,8,9,10,12-octahydro-1H-dibenzo[b,h]fluoren-12-yl)(phenyl)methyl)phenoxy)ethane

1,2-bis(4-(cyclopenta-2,4-dien-1-ylidene(phenyl)methyl)phenoxy)ethane) prepared in step 2 in a 100 mL Schlenk flask (1.48 g, 2.85 mmol) ), MTBE (13.0 mL) was added. In another 100 mL Schlenk flask, put lithium octahydrooctamethylfluorene (2.0 g) and MTBE (26.0 mL), and 1,2-bis(4-(cyclopenta-2,4-dien-1-yl) at room temperature den (phenyl) methyl) phenoxy) ethane) was added dropwise to the contents of the flask. It was stirred at 50 °C overnight. After extraction using distilled water and diethyl ether, the final compound was obtained through recrystallization of methanol.

¹ H NMR (CDCl ₃ ): 7.65 to 6.26 (m, 34H), 5.35 (m, 4H), 4.24 (m, 4H), 1.72 (m, 16H), 1.26 (m, 48H)

Step 4: 1,2-bis(4-(cyclopenta-2,4-dien-1-yl(1,1,4,4,7,7,10,10-octamethyl-2,3,4, Preparation of 7,8,9,10,12-octahydro-1H-dibenzo[b,h]fluoren-12-yl)(phenyl)methyl)phenoxy)ethane-hafnium chloride

1,2-bis(4-(cyclopenta-2,4-dien-1-yl(1,1,4,4,7,7,10,10-octamethyl-2, 3,4,7,8,9,10,12-octahydro-1H-dibenzo[b,h]fluoren-12-yl)(phenyl)methyl)phenoxy)ethane (2.44 g, 1.89 mmol); Toluene (18.2 ml) and THF (1.8 ml) were added. At -20°C, n-BuLi (3.1 mL) was slowly added dropwise, and the mixture was stirred at room temperature overnight. HfCl (1.21 g) was slowly added dropwise at -20°C, and stirred at 60°C overnight. The solvent was vacuum dried and extracted with hexane and methylene chloride (MC) to obtain the final compound.

¹ H NMR (CDCl ₃ ): 8.04-7.00 (m, 34H), 4.32 (m, 4H), 1.67-0.84 (m, 64H)

Preparation Example 2: Preparation of Ligand Compound and Transition Metal Compound

Step 1: Preparation of ethane-1,2-diylbis(4,1-phenylene))bis(phenylmethanone)

1,2-diphenylethane (5.0 g, 27.4 mmol), AlCl ₃ (8.05 g), and 1,2-dichloroethane (98.0 mL) were placed in a 100 mL Schlenk flask. Benzoyl chloride (2.05 eq, 7.90 g) was slowly added dropwise at room temperature. Stir overnight at 65°C. Then, the final compound was obtained by extraction using ice water, 10% HCl, and distilled water.

¹ H NMR (CDCl ₃ ): 7.80 (m, 18H), 3.73 (s, 4H)

Step 2: Preparation of 1,2-bis(4-(cyclopenta-2,4-dien-1-ylidene(phenyl)methyl)phenyl)ethane

Ethane-1,2-diylbis(4,1-phenylene))bis(phenylmethanone) prepared in step 1 in a 100 mL Schlenk flask (6.36 g, 16.3 mmol), pyrrolidine (4.1 mL) and THF (15.4 mL). Cyclopentadienide (sodium Cp) (2.0 M, 48.8 mL) was slowly added dropwise at room temperature and stirred at room temperature overnight. After extraction using distilled water and diethyl ether, the final compound was obtained through recrystallization of methanol.

¹ H NMR (CDCl ₃ ): 7.39-7.20 (m, 18H), 6.60 (m, 4H), 6.33 (m, 4H), 3.48 (s, 4H)

Step 3: 1,2-bis(4-(cyclopenta-2,4-dien-1-yl(1,1,4,4,7,7,10,10-octamethyl-2,3,4, Preparation of 7,8,9,10,12-octahydro-1H-dibenzo[b,h]fluoren-12-yl)(phenyl)methyl)phenyl)ethane

1,2-bis(4-(cyclopenta-2,4-dien-1-ylidene(phenyl)methyl)phenyl)ethane (1.38 g, 2.83 mmol) prepared in step 2 above in a 100 mL Schlenk flask , MTBE (13.0 mL) was added. In another 100 mL Schlenk flask, put lithium octahydrooctamethylfluorene (2.0 g) and MTBE (26.0 mL), and 1,2-bis(4-(cyclopenta-2,4-dien-1-yl) at room temperature The contents of the flask containing den(phenyl)methyl)phenyl)ethane were added dropwise. Stir overnight at 50°C. After extraction using distilled water and diethyl ether, the final compound was obtained through recrystallization of methanol.

¹ H NMR (CDCl ₃ ): 7.69-6.30 (m, 34H), 5.41 (m, 4H), 3.78 (m, 4H), 1.64 (m, 16H), 1.28 (m, 48H)

Step 4: 1,2-bis(4-(cyclopenta-2,4-dien-1-yl(1,1,4,4,7,7,10,10-octamethyl-2,3,4, Preparation of 7,8,9,10,12-octahydro-1H-dibenzo[b,h]fluoren-12-yl)(phenyl)methyl)phenyl)ethane-hafnium chloride

1,2-bis(4-(cyclopenta-2,4-dien-1-yl(1,1,4,4,7,7,10,10-octamethyl-2, 3,4,7,8,9,10,12-octahydro-1H-dibenzo[b,h]fluoren-12-yl)(phenyl)methyl)phenyl)ethane (2.05 g, 1.63 mmol), toluene (29.6 mL) and THF (3.0 mL) were added. At -20°C, n-BuLi (2.67 mL) was slowly added dropwise, and the mixture was stirred at room temperature overnight. HfCl (1.04 g) was slowly added dropwise at -20°C, and stirred at 60°C overnight. The solvent was vacuum dried and extracted with hexane and methylene chloride to obtain the final compound.

¹ H NMR (CDCl ₃ ): 8.05-7.17 (m, 34H), 3.76 (m, 4H), 1.72-0.85 (m, 64H)

Example 1

After charging a 1.5 L continuous process reactor with hexane solvent (7 kg/h) and 1-butene (0.87 kg/h), the temperature at the top of the reactor was preheated to 150°C. Modified methylaluminoxane (MMAO) (0.07 mmol/min), the transition metal compound obtained in Preparation Example 1 (0.055 μmol/min), and dimethylanilinium tetrakis (pentafluorophenyl) borate cocatalyst (0.17 μmol/min) ) were simultaneously introduced into the reactor. Then, hydrogen gas (20 cc/min) and ethylene (0.87 kg/h) were introduced into the reactor and maintained at 150° C. for 30 minutes or more in a continuous process at a pressure of 89 bar to proceed with a copolymerization reaction to 153 g/10 min. A copolymer was obtained in a yield of After drying in a vacuum oven for more than 12 hours, physical properties were measured.

Examples 2 to 5

The copolymerization reaction was carried out in the same manner as in Example 1, and the amount of the transition metal compound, the amount of catalyst and co-catalyst, and the reaction temperature, the amount of hydrogen input, and the amount of comonomer were respectively changed as shown in Table 1 below to proceed with the copolymerization reaction. synthesis was obtained.

Comparative Example 1

EG7447 from DOW was purchased and used.

Comparative Example 2

DF740 from Mitsui Chemicals was purchased and used.

Comparative Example 3

DF640 from Mitsui Chemicals was purchased and used.

Comparative Example 4

EG7467 from Dow was purchased and used.

Catalyst type Catalyst usage
(μmol/min) cocatalyst
(μmol/
min) MMAO
(mmol/min) ethylene
(kg/h) hexane
(Kg/h) 1-butene
(kg/h) Hydrogen
(cc/min) reaction temperature
(℃) yield
(g/10min) Example 1 Preparation Example 1 0.055 0.17 0.07 0.87 7 0.87 20 150 153 Example 2 Preparation Example 1 0.033 0.099 0.2 0.87 7 0.75 40 137 140 Example 3 Preparation Example 1 0.0385 0.1155 0.2 0.87 7 0.85 32 137 140 Example 4 Preparation Example 1 0.0405 0.1215 0.2 0.87 7 0.89 24 135 138 Example 5 Preparation Example 1 0.055 0.16 0.07 0.87 7 0.87 20 150 153

Experimental example

The copolymers of Examples 1 to 5 and Comparative Examples 1 to 4 were evaluated for physical properties according to the following method, and are shown in Tables 2 and 3 below.

1) Density of the polymer

Measured by ASTM D-792.

2) Melt Index (MI) of polymer

It was measured by ASTM D-1238 (Condition E, 190°C, 2.16 kg load).

3) Melt flow rate ratio (MFRR)

Measure MI10 and MI2.16 according to ASTM D-1238 [Condition E, MI10 (190℃, 10kg load), MI2.16(190℃, 2.16kg load)], then divide MI10 by MI2.16 to melt flow rate The ratio (MFRR) was calculated.

4) Melting temperature (Tm)

It was obtained using a differential scanning calorimeter (DSC: Differential Scanning Calorimeter 250) manufactured by TA Instruments. That is, after increasing the temperature to 150° C., maintaining it at that temperature for 1 minute, then lowering it to -100° C., and increasing the temperature again, the top of the DSC curve was used as the melting point. At this time, the rate of temperature rise and fall is 10° C./min, and the melting point is obtained while the second temperature rises.

5) Weight average molecular weight (Mw, g/mol) and molecular weight distribution (MWD)

The number average molecular weight (Mn) and the weight average molecular weight (Mw) were respectively measured using gel permeation chromatography (GPC), and the molecular weight distribution was calculated by dividing the weight average molecular weight by the number average molecular weight.

- Column: PL Olexis

- Solvent: TCB (Trichlorobenzene)

- Flow rate: 1.0 ml/min

- Sample concentration: 1.0 mg/ml

- Injection volume: 200 μl

- Column temperature: 160℃

- Detector: Agilent High Temperature RI detector

- Standard: Polystyrene (corrected by cubic function)

6) High-temperature melting peaks of polymers and T(95), T(90), T(50)

The differential scanning calorimeter (DSC: Differential Scanning Calorimeter 250) manufactured by TA Instruments was obtained using SSA (Successive self-nucleation/annealing) measurement method.

Specifically, the temperature was increased to 150°C in the first cycle, held at that temperature for 1 minute, and then cooled to -100°C. In the second cycle, the temperature was increased to 120 °C, held at that temperature for 30 minutes and then cooled to -100 °C. In the third cycle, the temperature was increased to 110 °C, held at that temperature for 30 minutes and then cooled to -100 °C. In this way, the process of raising the temperature at intervals of 10°C and cooling to -100°C was repeated until -60°C so that crystallization was performed for each temperature section.

In the last cycle, the heat capacity was specified while the temperature was increased to 150°C.

The temperature-heat capacity curve obtained in this way was integrated for each section to fractionate the heat capacity of each section compared to the total heat capacity. Here, the temperature at which 50% of the total is melted is defined as T(50), the temperature at which 90% is melted is defined as T(90), and the temperature at which 95% is melted is defined as T(95).

Fig. 1 shows the SSA graph of the polymer of Example 1, and Fig. 2 shows a graph obtained by fractionating the SSA result of the polymer of Example 1.

In addition, the SSA graph of the polymer of Comparative Example 1 is shown in FIG. 3, and the graph obtained by fractionating the SSA result of the polymer of Comparative Example 1 is shown in FIG. 4, respectively.

Comparing FIGS. 1 and 2 for Example 1 and FIGS. 3 and 4 for Comparative Example 1, the olefin-based polymer of Example 1 was 50% to 90% in a narrow temperature range compared to the olefin-based polymer of Comparative Example 1. It can be confirmed that melting is made.

6) Anti-blocking property evaluation

50 g of the prepared copolymer pellets were taken and placed in an 8 cm × 10 cm zipper bag, punctured with a needle to release air and compressed. A zipper bag was placed on the central part away from the bottom of the chamber, and a load was applied with a 2 kg weight × 2 on top. The chamber temperature program was started and maintained at 45° C. for 11 hours and then maintained at -10° C. for 11 hours. This temperature program was repeated 3 times.

Afterwards, the degree of blocking was confirmed with IMADA's digital force gauge (model name: DS2-500N). The required force was measured while removing the zipper bag and disintegrating the blocked sample with a force gauge. At this time, the smaller the required force, the smaller the degree of blocking, so it can be seen that the anti-blocking property is excellent.

density
(g/mL) MI
(g/
10min) MFRR DSC Mw
(g/mol) MWD SSA Tm
(℃) T(50) T(90) T(95) T(95)-T(90) T(90)-T(50) Example 1 0.8668 4.38 6.58 41.60 80544 2.063 27.1 52.2 57.5 5.3 25.1 Example 2 0.8703 3.46 6.44 44.65 82030 2.040 35.5 61.0 67.3 6.3 25.5 Example 3 0.8638 3.44 6.43 35.70 88376 2.040 22.2 48.8 54.4 5.6 26.6 Example 4 0.8639 1.24 6.50 35.30 110524 2.015 22.5 47.5 53.0 5.5 25.0 Example 5 0.8688 4.44 6.70 35.60 80364 2.065 34.8 60.6 66.9 6.3 25.8 Comparative Example 1 0.8690 4.82 6.85 42.90 74120 2.040 23.2 54.6 61.9 7.3 31.4 Comparative Example 2 0.8700 3.52 6.51 51.28 81884 1.960 29.5 57.5 64.0 6.5 28.0 Comparative Example 3 0.8627 4.03 6.22 38.63 82248 1.940 21.5 54.2 57.8 3.6 32.7 Comparative Example 4 0.8660 1.25 7.30 38.40 109775 2.060 17.0 46.4 54.6 8.2 29.4

density
(g/mL) MI
(g/10min) DSC SSA blocking evaluation
(N) Tm
(℃) T(95)
-T(90) T(90)
-T(50) Example 1 0.8668 4.38 41.60 5.3 25.1 4.2 Example 2 0.8703 3.46 44.65 6.3 25.5 3.0 Example 3 0.8638 3.44 35.70 5.6 26.6 3.6 Example 4 0.8639 1.24 35.30 5.5 25.0 11.2 Example 5 0.8688 4.44 35.60 6.3 25.8 5.1 Comparative Example 1 0.8690 4.82 42.90 7.3 31.4 30.5 Comparative Example 2 0.8700 3.52 51.28 6.5 28.0 40.6

Referring to Tables 2 and 3, the olefin-based polymers of Examples 1 to 5 have smaller T(90)-T(50) values compared to the olefin-based polymers of Comparative Examples 1 to 4 having the same level of density and MI. , and the T(95)-T(90) value also showed a small value. As a result, it was confirmed that the olefin-based polymers of Examples 1 to 5 had a narrow distribution of crystalline regions compared to the olefin-based polymers of Comparative Examples 1 to 4 having the same density and MI.

As such, the olefin-based polymers of Examples 1 to 5, in which the distribution of the crystalline region of the olefin-based polymer is narrow, may exhibit excellent anti-blocking properties, and the olefin-based polymers of Examples 1 to 5 and Comparative Examples 1 and 4 of Table 3 Through the blocking evaluation, it was possible to confirm the difference in the effect of the anti-blocking characteristic.

Claims (12)

Olefin-based polymers satisfying the requirements of (1) to (4) below:
(1) Melt Index (MI, 190 ℃ 2.16 kg load condition) is 0.1 g/10 min to 10.0 g/10 min,
(2) the density (d) is from 0.855 g/cc to 0.880 g/cc,
(3) the melting temperature (Tm) obtained from the DSC curve obtained by measuring with a differential scanning calorimeter (DSC) is 30 ℃ to 60 ℃,
(4) 20≤T(90)-T(50)≤27, and 4.5≤T(95)-T(90)≤7.0 in differential scanning calorimetry precision measurement (SSA),
where T(50), T(90) and T(95) are respectively 50%, 90%, and 95% melting when the temperature-heat capacity curve is fractionated from the differential scanning calorimetry precision measurement (SSA) measurement result, respectively. is the temperature
The method of claim 1,
The olefin-based polymer further satisfies the requirement of (5) a weight average molecular weight (Mw) of 10,000 g/mol to 500,000 g/mol.
The method of claim 1,
The olefin-based polymer further satisfies the requirement of (6) a molecular weight distribution (MWD) of 0.1 to 6.0.
The method of claim 1,
The olefin-based polymer further satisfies the requirement of (7) a melt flow rate ratio (MFRR) of 3 to 7.
The method of claim 1,
The olefin-based polymer has a melt index (MI) of 0.1 g/10 min to 6.5 g/10 min.
The method of claim 1,
The olefin-based polymer is 23≤T(90)-T(50)≤27, and 5≤T(95)-T(90)≤7 when measured by differential scanning calorimetry (SSA).
The method of claim 1,
The olefin-based polymer is a copolymer of ethylene and an alpha-olefin comonomer having 3 to 12 carbon atoms, the olefin-based polymer.
8. The method of claim 7,
The alpha-olefin comonomer is propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene , 1-tetradecene, 1-hexadecene, 1-aitocene, norbornene, norbornadiene, ethylidene noboden, phenyl noboden, vinyl noboden, dicyclopentadiene, 1,4-butadiene, 1,5 -pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, and 3-chloromethylstyrene containing any one or a mixture of two or more selected from the group consisting of, an olefinic polymer.
The method of claim 1,
The olefin-based polymer is a copolymer of ethylene and 1-butene, the olefin-based polymer.
The method of claim 1,
The olefin-based polymer is an olefin-based polymer obtained by a manufacturing method comprising the step of polymerizing an olefin-based monomer by introducing hydrogen gas in the presence of a catalyst composition for olefin polymerization comprising a transition metal compound of Formula 1 below:
[Formula 1]

In Formula 1,
R ₁ to R ₁₃ are each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; alkoxy having 1 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; arylalkoxy having 7 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; arylalkyl having 7 to 20 carbon atoms; silyl; or silyl having 1 to 3 substituents selected from the group consisting of alkyl having 1 to 12 carbon atoms and alkoxy having 1 to 12 carbon atoms, wherein _{two or more adjacent to each other among R 1} to R ₁₂ are connected to each other to form a ring can,
X and X' are each independently O, S or a linking group,
A is alkylene having 1 to 6 carbon atoms,
Y is C or Si,
M is a group 4 transition metal,
Q is hydrogen; halogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; arylalkyl having 7 to 20 carbon atoms; alkylamino having 1 to 20 carbon atoms; or arylamino having 6 to 20 carbon atoms.
11. The method of claim 10,
The olefin-based polymer obtained by the production method in which the amount of the hydrogen gas is 10 to 60 sccm.
11. The method of claim 10,
The olefin-based polymer is prepared by a continuous solution polymerization reaction using a continuous stirred tank reactor (Continuous Stirred Tank Reactor) by adding hydrogen in the presence of the catalyst composition for olefin polymerization, the olefin-based polymer.

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